Copper-containing azodyestuff



Patented Aug. 8, 1933 entree STATES-# PA oFHc g COPPER-CONTAINING AzoDYEsTUFr Karli Wiedemann, Leverkusen Il G1 Werk and" Heinrich Clingestein, Cologne-on-th'e-Rhine; Germany, ,assignors to General; Amline Works,

Inc.,' New York, N:

ware 1 Y., a;Go1-poration.of- Dela.-

No Drawing- Application August 5; 1982;;Serial No. 0271372, and in Germany September 21;

The present inventionrelates'to new azodye representedby thezgeneral formula:

ing one molecular proportion of a 4.4'-diaminodiphenyl, the corresponding urea or thiourea containing in o-position to each amino group an alkoxy group or a carboxylic acid group,- coupling with two molecular proportions of a dihydroxynaphthalene-mono-or-disulfonic acid, one hydroxy group of which may be etherified by alkyl,

and treating the disazodyestuff thus obtained with an agent yielding copper. In case there are coppered such dyestuifs which contain an alkoxygroup in o-position to each azo-group coppering is performed under such conditions that the alkoxy group is split up; this can be achieved for example by working at elevated temperatures and under superatmospheric pressure or by coppering with the addition of an organic base or ammonia.

Our new dyestufis are in form of their alkali metal salts generally dark powders, dyeing cotton generally violet to blue shades of excellent fastness to light.

The invention is illustrated bythe following examples, without being limited thereto:

5Q; Example 1. 27,2 parts by weight of 4. 4'-di- 3Claims. (onto-fir aminodiphenyP-313" dicarboxylic' acid are tetra zotized and coupled with 48 parts by Weight of 225-dihydroxynaphthalene-7-sulfonic acid in .aqueous soda alkaline solution. The dyestuif is dyes cotton from an alkaline bath bluish-violet shades very fast to light and ironing.

Example 2.--24,4 parts by weight of 4.4'-di- -amino-3.3-dimethoxydiphenyl are tetrazotized and coupled in an alkaline solution with 64 parts by weight of 1.8-dihydroxynaphthalene-3.6-disulfonic acid. The dyestuff is isolated, re-dissolved and treated for 5 hours with an ammoniacal solution prepared from parts by weight of crystallized copper sulfate at a temperature of C., salted out and driedat C. The dyestuff having in its free state the following formula:

O 011 -O OH 803K Hons SO3H dyes cotton and viscose blue shades of good fastness to light and ironing.

Example 3.30,2 parts by weight of 4.4'-diamino-3.3-dimethoxy-diphenylurea are coupled in soda alkaline solution in 48 parts by weight of 2.8-dihydroxynaphthalene-6 sulfonic acid. The

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dyestufi is isolated, re-dissolved'and treated for about 2 hours at C. with an ammoniacal solution prepared from 50 parts by weight of crystallized copper sulfate. The dyestuff thus obtained dyes cotton reddish-blue shades of excellent fastness to light.

Example 4.30,2 parts by weight of 4.4'-diamino-3.3-dimethoxydiphenylurea are coupled in soda alkaline solution with 69,6 parts by weight of 1-ethoxy-8-hydroxynaphthalene-3.G-disulfonic acid and the dyestuff is coppered as described in Example 3. The copper-containing dyestuff thus obtained dyes cotton bluish-violet shades of I excellent fastness to light.

The same dyestuff is also obtainable by coupling one molecular proportion of 5-nitro-2- amino-l-anisol with one molecular proportion of 1-ethoxy-8-hydroxynaphthalene 3.6 disulionic acid, reducing the nitro group to form the amino group, transforming into the corresponding urea by treating with phosgen and performing the coppering as described in paragraph 1.

A dyestuif having similar properties is obtained when using as tetrazotization component 4.4- diamin0-3 .3 -dimethoxydiphenylthiourea.

OHO

We claim: 1. As new products copper-containing azodyenaphthalene nucleus in o-position to the azo group, being in form of their alkali metal salts generally dark'powders, dyeing cotton generally violet to blue shades of excellent fastness to light.

2. As a new product the copper-containing azodyestufi of the following formula:

in which the azo-bridge is attached to the naphthalene nucleus in o-position to one of the hydroxy groups, dyeing cotton bluish-violet shades of excellent fastness to light and ironing.

3. As a new product the copper-containing azodyestuff of the following formula:

dyeing cotton and yiscose blue shades of good fastness to light and ironing.

stuffs of the probable general formula: KARL WIEDEMANN.

HEINRICH CLINGESTEIN.

2O v Oz N=N' zON=N- (3031 1) (80:11) 0 

